Tetrahydrofuran derivative and herbicide containing the same as active ingredient

ABSTRACT

A tetrahydrofuran derivative represented by the following general formula [I]: ##STR1## [wherein A represents direct bonding or a group represented by --B--CHR 1  -- (wherein B represents oxygen atom, sulfur atom or imino group; R 1  represents hydrogen atom or an alkyl group); R represents hydrogen atom, halogen atom, hydroxyl group, an alkoxy group, benzyloxy group, an alkylsulfonyloxy group or a group represented by --O--COR 2  (wherein R 2  represents an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, phenyl group, benzyl group, an alkoxy group, an alkylamino group or a dialkylamino group; X represents halogen atom; Y represents hydrogen atom or halogen atom) and the herbicide containing the same as the effective ingredient. The compounds of the present invention have exceedingly high herbicidal activity, and furthermore, the compounds are superior to the known similar compounds in terms of safety on crops. Thus, the compounds are useful as herbicides.

This application is a division of application Ser. No. 07/979,231, filedNov. 20, 1992, now U.S. Pat. No. 5,324,709.

FIELD OF THE INVENTION

The present invention relates to a novel tetrahydrofuran derivative anda herbicide containing the same as the active ingredient.

BACKGROUND OF THE INVENTION

As herbicides, proposition has been made of heterocyclic compoundssubstituted with phenyl groups having certain types of substituents,such as N-(substituted phenyl)-3, 4, 5, 6-tetrahydrophthalimides,3-(substituted phenyl)-1, 5-tetramethylenehydantoins, 4-(substitutedphenyl)-1, 2-tetramethyleneurazoles, 9-(substitutedphenylimino)-8-thia-1, 6-diazabicyclo[4.3. 0]nonan-7-ones,3-(substituted phenyl)-1, 3, 4-oxadiazolin-2-ones and the like. However,these compounds generally have low selectivity between weeds and crops,so they cannot satisfy both of herbicidal activity and safety for crops.Thus, they are presently put to practical use only in a limited field.

Although a great number of substituted-phenyl heterocyclic compoundswith herbicidal activity have been proposed as has been described above,few of them have both the safety for significant crops and sufficientherbicidal activity, so that herbicides provided with the two propertieshave been expected. In case of taking account of environmental influenceas well, a herbicide with less dose for application is preferable.

The present inventors have made intensive investigations on the problemsdescribed above, and have found that certain specific compounds having atetrahydrofuran ring have characteristic properties such that thecompounds have high herbicidal activity and nevertheless do not showalmost any influence on a great number of significant crops. Thus, theyhave achieved the present invention.

That is, the gist of the present invention resides in noveltetrahydrofuran derivatives, represented by the following generalformula [I]: ##STR2## {wherein A represents direct bonding or a grouprepresented by --B--CHR¹ -- (wherein B represents oxygen atom, sulfuratom or imino group; R¹ represents hydrogen atom or an alkyl group of C₁-C₄);

R represents hydrogen atom, halogen atom, hydroxyl group, an alkoxygroup of C₁ -C₄, benzyloxy group, an alkylsulfonyloxy group of C₁ -C₃ ora group represented by --O--COR² (wherein R² represents an alkyl groupof C₁ -C₅, a haloalkyl group of C₁ -C₃, an alkenyl group of C₂ -C₅, acycloalkyl group of C₃ -C₆, phenyl group, benzyl group, an alkoxy groupof C₁ -C₄, an alkylamino group of C₁ -C₄ or a dialkylamino group of C₂-C₆);

X represents halogen atom;

Y represents hydrogen atom or halogen atom;

Z is a group represented by ##STR3## (wherein U¹, U² and U³independently represent oxygen atom or sulfur atom; R³, R⁴, R⁵, R⁶, R⁷and R⁸ independently represent an alkyl group of C₁ -C₄)}; and aherbicide containing the same as the active ingredient.

The compounds of the present invention will now be explained in details.

In accordance with the present invention, the tetrahydrofuranderivatives to be used as a herbicide is represented by the abovegeneral formula [I].

In the above general formula [I], A represents direct bonding or a grouprepresented by --B--CHR¹ -- (wherein B represents O, S or NH; R¹represents hydrogen atom or an alkyl group of C₁ -C₄ such as methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group andthe like).

R represents hydrogen, atom; halogen atom such as fluorine atom,chlorine atom, bromine atom and the like; hydroxyl group; an alkoxygroup of C₁ -C₄ such as methoxy group, ethoxy group, n-propoxy group,isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group,t-butoxy group and the like; benzyloxy group; an alkylsulfonyloxy groupof C₁ -C₃ such as methylsulfonyloxy group, ethylsulfonyloxy group,n-propylsulfonyloxy group, isopropylsulfonyloxy group, and the like; ora group represented by --O--COR² (wherein R² represents an alkyl groupof C₁ -C₅ such as methyl group, ethyl group, n-propyl group, isopropylgroup, n-butyl group, isobutyl group, sec-butyl group, t-butyl group,n-pentyl group, isopentyl group, neopentyl group, t-pentyl group,1-methylbutyl group, 2-methylbutyl group, 1-ethylpropyl group,1,2-dimethylpropyl group and the like; a haloalkyl group of C₁ -C₃ suchas chloromethyl group, bromomethyl group, 2-chloroethyl group,2-bromoethyl group, 3-chloropropyl group, 3-bromopropy group,difluoromethyl group, dichloromethyl group, trifluoromethyl group,trichloromethyl group, 2, 2, 2-trifluoroethyl group and the like; analkenyl group of C₂ -C₅ such as vinyl group, allyl group, 1-propenylgroup, 1-methylvinyl group, 2-butenyl group, 3-butenyl group,1-methylallyl group, 2-methylallyl group, 2-pentenyl group, 3-pentenylgroup, 4-pentenyl group, 3-methyl-2-butenyl group, 2-methyl-3-butenylgroup, 4-pentenyl group, 3-methyl-2-butenyl group, 2-methyl-3-butenylgroup, 3-methyl-3-butenyl group, 1-methyl-2-butenyl group,1-methyl-3-butenyl group and the like; a cycloalkyl group of C₃ -C₆ suchas cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexylgroup and the like; phenyl group; benzyl group; an alkoxy group of C₁-C₄ such as those described above as the R; an alkylamino group of C₁-C₄ such as methylamino group, ethylamino group, n-propylamino group,isopropylamino group, n-butylamino group, isobutylamino group,secbutylamino group, t-butylamino group and the like; or a dialkylaminogroup of C₂ -C₆ such as dimethylamino group, diethylamino group,di-n-propylamino group, diisopropylamino group, methylethylamino group,methyl-n-propylamino group and the like.

X represents halogen atom such as those as described above as the R; Yrepresents hydrogen atom or halogen atom such as those described aboveas the R. Z is a group represented by ##STR4## (wherein U¹, U² and U³independently represent oxygen atom or sulfur atom; R³, R⁴, R⁵, R⁶, R⁷and R⁸ independently represent an alkyl group of C₁ -C₄ such as methylgroup, ethyl group, n-propyl group, isopropyl group, n-butyl group,isobutyl group, sec-butyl group, t-butyl group and the like).

The compounds of the present invention are preferably ones wherein Rrepresents hydrogen atom, hydroxyl group, benzyloxy group, analkylsulfonyloxy group of C₁ -C₃ or a group represented by --O--COR²(wherein R² represents an alkyl group of C₁ -C₅, a haloalkyl group of C₁-C₃, an alkenyl group of C₂ -C₅, a cycloalkyl group of C₃ -C₆, phenylgroup, and an alkoxy group of C₁ -C₄ [in particular, R more preferablyrepresents hydrogen atom, hydroxyl group or an alkylsulfonyloxy group ofC₁ -C₃, or a group represented by --O--COR² group (wherein R² representsan alkyl group of C₁ -C₅, an alkenyl group of C₂ -C₅, a cycloalkyl groupof C₃ -C₆, a phenyl group or an alkoxy group of C₁ -C₃)]; and Zrepresents a group represented by ##STR5## (wherein U¹ and U²independently represent oxygen atom or sulfur atom; R³ represents analkyl group of C₁ -C₃). (As Z, the one representing ##STR6## ispreferable.)

More preferable compounds are ones wherein A represents --SCH₂ --; Rrepresents a group represented by --O--COR² (wherein R² represents analkyl group of C₁ -C₅); X and Y represent halogen atom; and Z represents##STR7## Particularly preferable compounds include9-(5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethylthio)-4-chloro-2-fluorophenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan7-one (Compound No. 26 in Table 1 describedbelow) shown in Example 11 described below.

The method for producing the compounds of the present invention will nowbe explained below.

The compounds of the present invention represented by the above generalformula [I], can be synthesized, for example, by the following reactionscheme. ##STR8## (In the above reaction scheme, V¹ represents halogenatom such as chlorine atom, bromine atom and the like; A, R, X, Y, and Zindependently represent the same meanings as described above.)

The above reaction is carried out without a solvent or in a solvent inthe presence or absence of a base, generally in a temperature range of0° to 100 ° C. Appropriate solvent if used includes aromatichydrocarbons such as benzene, toluene, xylene and the like; halogenatedhydrocarbons Such as dichloromethane, chloroform, 1, 2-dichloroethaneand the like; ethers such as diethyl ether, tetrahydrofuran, dioxane andthe like; esters such as methyl acetate, ethyl acetate and the like;ketones such as acetone, methyl ethyl ketone and the like; polarsolvents such as N, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile and the like. The bases to be used includetriethylamine, pyridine, picoline, N, N-dimethylaniline, sodiumhydrogencarbonate, potassium hydrogen carbonate, sodium carbonate,potassium carbonate, sodium hydroxide, potassium hydroxide, sodiummethylate, sodium ethylate, sodium hydride and the like.

The starting material compound [II] can be produced by reacting thecorresponding carboxylic acid XI] with a halogenating agent such asthionyl chloride, phosphorous trichloride, phosphorous tribromide andthe like. The compound [XI] is described in each gazette of JapanesePatent Laid-open Nos. 149267/1982, 189178/1983, 225070/1983,109578/1985, 149571/1985, and 76487/1986, European Patent PublicationNos. 49508, 77938 and 126419. ##STR9## (In the above scheme, A, X, Y, Z,and V¹ independently represent the same meanings as described above.)##STR10## (In the above reaction scheme, V² represents halogen atom suchas chlorine atom, bromine atom and the like; A, R², X, Y, and Zindependently represent the same meanings as described above.)

The above reaction is carried out without a solvent or in a solvent inthe presence of a base, generally in a temperature range of 0° to 100 °C. Appropriate solvent if used includes those described in (1). Thebases to be used include those described in (1).

The starting material [IV] is a compound wherein R is hydroxyl group inthe compound [I] of the present invention, and can be produced by themethods shown in the process (1) described above, and the processes (3),(4), (5), (6) and (7) described below. ##STR11## (In the above reactionscheme, A, X, Y, Z and V² independently represent the same meanings asdescribed above; and R⁹ represents an alkyl group of C₁ -C₃ such asmethyl group, ethyl group, n-propyl group, isopropyl group.)

The above reaction is carried out without a solvent or in a solvent inthe presence of a base, generally in a temperature range of 0° to 100 °C. Appropriate solvent if used includes those described in (1). Thebases to be used include those described in (1). ##STR12## (In the abovereaction scheme, V³ represents halogen atom such as chlorine atom,bromine atom, iodine atom; B, R, R¹, X, Y and Z independently representthe same meanings as described above.)

The above reaction is carried out without a solvent or in a solvent inthe presence of a base, generally in a temperature range of roomtemperature to 200° C. Appropriate solvent if used includes thosedescribed in (1), and besides, the bases to be used include thosedescribed in (1).

In case V³ means Cl or Br, iodide such as sodium iodide, potassiumiodide, and the like may be added to acclerate the reaction.

The starting material IV] is described in each gazette of JapanesePatent Laid-open Nos. 53662/1981, 83672/1983, 189178/1983, 172491/1984,109578/1985, 149571/1985, 233075/1985, 40261/1986, and 76487/1986,European Patent Publication No. 77938 and United Kingdom PatentPublication No. 2127410. ##STR13## (In the above reaction scheme, A, R,X, and Y independently represent the same meanings as described above.)

The above reaction is carried out without a solvent or in a solventunder heating, generally in a temperature range of 50° to 200 ° C.Appropriate solvent if used includes water; and polar solvents includingcarboxylic acids such as acetic acid, alcohols such as methanol,ethanol, propanol, butanol, etc.; and the like, in addition to thesedescribed in (1).

The starting material [VII] can be produced, for example, by the methodshown in the following scheme. ##STR14## (In the above scheme, A, B, R,R¹, X and Y independently represent the same meanings as describedabove.) ##STR15## (In the reaction scheme, A, R, X, Y, and R³independently represent the same meaning as described above.)

The above reaction is carried out without a solvent or in a solvent,generally in a temperature range of 0° to 100 ° C. Appropriate solventif used includes those described in (1).

The starting material [VIII] can be produced by reacting the compound[VII] described hereinabove with thiophosgene or N,N-dialkylthiocarbamoyl chloride. ##STR16## (In the scheme, A, R, X and Yindependently represent the same meanings as described above; R¹¹represents a lower alkyl group such as methyl group, ethyl group, propylgroup, butyl group and the like). ##STR17## (In the above reactionscheme, R¹⁰ represents hydrogen atom or an alkyl group of C₁ -C₄ such asmethyl group, ethyl group, propyl group, butyl group and the like; Drepresents --N-- or --CH--; A, R, X, Y and U¹ independently representthe same meanings as described above.)

The above reaction is carried out without a solvent or in a solvent inthe presence or absence of a base, generally in a temperature range ofroom temperature to 200 ° C. Appropriate solvent if used includes polarsolvents such as alcohols such as methanol, ethanol, propanol and thelike; water and the like, in addition to those described in (1). Thebases to be used include those described in (1).

The starting material [IX] can be produced from the compound [VII]described above, for example, by the method shown in the followingscheme. In the scheme, phosgene or trichloromethyl chloroformate is usedfor the preparation of isocyanate (U¹ =O) in the reaction of the firststage. And, thiophosgene or N, N-dialkylthiocarbamoyl chloride is usedfor the preparation of isothiocyanate (U¹ =S). ##STR18## (In the scheme,A, R, X, Y, U¹, D and R¹⁰ independently represent the same meanings asdescribed above.) ##STR19## (In the above reaction scheme, A, R, X, Yand U² independently represent the same meanings as described above.)

The above reaction is carried out by reacting phosgene (U² =O) orthiophosgene (U² =S) without a solvent or in a solvent in the presenceof a base, generally in a temperature range of -10° to 100 ° C. In caseof U² =O, trichloromethyl chloroformate can be used instead of phosgene.Appropriate solvent if used includes those descried in (1). The bases tobe used include those described in (1).

The starting material [X] can be produced by reacting the compound[VIII] described above with hexahydropyridazine. ##STR20## (In the abovescheme, A, R, X and Y independently represent the same meanings asdescribed above.)

The compounds of the present invention thus obtained have isomers suchas optical isomers, diastereomer and the like. The present inventionincludes all of them. The compounds of the present invention can be usedas a herbicides singly as in the form of each of the isomers thereof oras an appropriate mixture of the isomers.

In using the compounds of the present invention as a herbicide, thetechnical product may be applied as it is. However, the compound isgenerally used in the form of wettable powder, granule, emulsifiableconcentrate, flowable and the like by using appropriate auxiliaries.Example of such auxiliaries include solid carrier such as kaolin,bentonite, talc, diamatoceous earth, white carbon, carbohydrate and thelike; solvents including water, alcohols (methanol, ethanol, propanol,butanol, ethylene glycol and the like), ketones (acetone, methyl ethylketone, cyclohexanone and the like), ethers (diethyl ether, dioxane,cellosolves and the like), aliphatic hydrocarbons (kerosin, kerosene,and the like), aromatic hydrocarbons (benzene, toluene, xylene, solventnaphtha, methylnaphthalene and the like), halogenated hydrocarbon(dichloroethane, trichlorobenzene, carbon tetrachloride and the like),amides (dimethylformamide and the like), esters (ethyl acetate, butylacetate, fatty acid glycerin esters and the like), nitriles(acetonitrile and the like); surfactant including nonionic surfactant(polyoxyethylene alkylallyl ether, polyoxyethylene sorbitan monolaurateand the like), cationic surfactant (alkyl dimethylbenzylammoniumchloride, alkylpyridium chloride and the like), anionic surfactant(alkylbenzene sulfonate, lignin sulfonate, higher alcohol sulfate andthe like), amphoteric surfactant (alkyl dimethyl betaine,dodecylaminoethyl glycine and the like), and the like. These solidcarriers, solvents, and surfactants are individually used in a mixtureof one or two or more thereof, depending on needs.

The dose for application of the compounds of the present inventionvaries depending on the structure of the compound, the subjective weeds,the application time, the application method, the soil properties andthe like, but the dose as the active ingredient thereof is generally ina range of 5-2000 g, preferably 10-1000 g per ha.

The subjective weeds of the compounds of the present invention are, forexample, Chenopodium album, Chenopodium serotinum, Polygonumlapathifolium, Polygonum persicaria, Amaranthus lividus, Amaranthusviridis, Stellaria media, Lamium amplexicaule, Digitaria adscendens,Eleusine indica, Echinochloa Crus-galli, Setaria viridis, and the likein upland fields; in paddy fields, for example, Rotala indica, Linderniapyridaria, Monochoria vaginalis, Dopatrium junceum, Elatine triandra,Alisma canadiculatum, Echinochloa oryzicola, Cyperus difformis, and thelike. Furthermore, the compounds of the present invention exhibits highherbicidal activity on those weeds which have been hard to be controlledby known herbicides, including, for example, Abutilon theophrasti,Xanthium strumarium, Ipomoea indica, Datura Stramonium, Brassica juncea,Galium aparine, Viola tricolor, Matricaria matricarioides, Bidenspilosa, and the like in upland fields; in paddy fields, for example,Sagittaria pygmaea, Sagitaria trifolia, Scirpus juncoides, Cyperusserotinus, and the like. The compounds of the present invention showherbicidal activity against the weeds described above through the soilapplication in pre-emergent stage and the foliar application inpost-emergent stage. The compound of the present invention also haveless influence on crops such as corn, wheat, barley, sorgho, rice,soybean, potato and the like through soil application in pre-emergentstage and foliar application in post-emergent stage, and can be used asa selective herbicide.

The herbicide containing the compound of the present invention as theactive ingredient can be mixed and applied with other pesticides suchas, for example, insecticides, fungicides, plant growth regulators, orfertilizers. By mixing and applying with other herbicides, theherbicidal activity of the compound can be stabilized. The herbicideswhich can preferably be mixed with, include the following, for example:

Pyrazole herbicides; 4-(2, 4-dichlorobenzoyl)-1, 3-dimethylpyrazol-5-ylp-toluenesulfonate, 4-(2, 4-dichlorobenzoyl)-1,3-dimethyl-5-phenacyloxypyrazole, 4-(2,4-dichloro-3-methylbenzoyl)-1,3-dimethyl-5-(4-methylphenacyloxy)pyrazole,4-(2, 4-dichlorobenzoyl)-1-methyl-5-phenacyloxypyrazole, and the like;

Sulfonylurea herbicides; methyl 2-(4,6-dimethoxypyridin-2-ylcarbamoylaminosulfonylmethyl)benzoate, ethyl5-(4,6-dimethoxypyridin-2-ylcarbamoylaminosulfonyl)-1-methylpyrazole-4-carboxylate,2-chloro-N-(4-methoxy-6-methyl-1, 3, 5-triazin-2-ylaminocarbonyl)benzenesulfonamide, methyl 2-(4-methoxy-6-methyl-1, 3,5-triazin-2-ylcarbamoylaminosulfonyl)benzoate, methyl 2-(4,6-dimethylpyridin-2-ylcarbamoylaminosulfonyl)benzoate, ethyl2-(4-chloro-6-methoxypyridin-2-ylcarbamoylaminosulfonyl)benzoate, andthe like;

Phenoxy herbicides; (2, 4-dichlorophenoxy)acetate and the derivativesthereof, (4-chloro-2-methylphenoxy)acetate and the derivatives thereof,4-(4-chloro-2-methylphenoxy)butylate and the derivatives thereof,S-ethyl 4-chloro-2-methylphenoxy)thioacetate, 2-(2-naphthoxy)propioneanilide, 2-(2, 4-dichloro-3-methylphenoxy)propione anilide, butyl2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionate;

Haloacetanilide herbicides; 2-chloro-2',6'-diethyl-N-methoxymethylacetanilide,2-chloro-2',6'-diethyl-N-butoxymethylacetanilide,2-chloro-2'-ethyl-6'-methyt-N-(2-methoxy-1-methylethyl)acetanilide,2-chloro2',6'-diethyl-N-propoxyethylacetanilide, ethylN-chloroacetyl-N-(2, 6-diethylphenyl)aminoacetate,2-chloro-2',6'-dimethyl-N-(3-methoxy-2-tenylmethyl)acetanilide and thelike;

Amide herbicides; 3',4'-dichloropropionanilide,2',3'-dichloro-4-ethoxymethoxybenzanilide,2-bromo-3,3-dimethyl-N-(α,α-dimethylbenzyl)butylic acid amide,2-benzothiazol-2-yloxy-N-methylacetanilide,2',4'-difluoro-2-(3-trifluoromethylphenoxy)nicotinanilide,2,6-dimethoxy-N(3-(1-ethyl-1-methylpropyl)isoxazol-5-yl)benzamide, andthe like;

Carbamate herbicides; S-(4-chlorobenzyl) N,N-diethylthiocarbamate,S-ethyl N,N-hexamethylenethiocarbamate, S-isopropylN,N-hexamethylenethiocarbamate, S-benzylN-ethyl-N-(1,2-dimethylpropyl)thiocarbamate, S-(1-methyl-1-phenetyl)piperidine 1-carbothioate, O-(3-t-butylphenyl)N-(6-methoxypyridin-2-yl)-N-methylthiocarbamate, S-ethylN,N-di(n-propylthiol carbamate), S-ethyl N,N-diisobutylthiocarbamate,isopropyl N-(3-chlorophenyl)carbamate, 3-(methoxycarbonylamino)phenylN-(3-methylphenyl)carbamate, S-(2,3-dichloroallyl)N,N-diisopropylthiocarbamate, S-(2, 3, 3-trichloroallyl)N,N-diisopropylthiocarbamate, methyl N-(4-aminobenzenesulfonyl)carbamateand the like;

Urea herbicides; 1-(α,α-dimethylbenzyl)-3-(4-methylphenyl)urea,3-(benzothiazol-2-yl)-1,3-dimethylurea,3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea,3-(3,4-dichlorophenyl)-1,1-dimethylurea,3-[4-(4-methylphenetyloxy)phenyl]-1-methoxy-1-methylurea,3-(4-isopropylphenyl)-1,1-dimethylurea, 1-(2-substitutedbenzyl)-3-(α,α-dimethylbenzyl)ureas and the like;

Diphenyl ether herbicides; 2, 4, 6-trichloro-4'-nitrodiphenyl ether,2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether, methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate,3-[5-(2-chloro-4-trifluoromethylphenoxy)2-nitrophenoxy]tetrahydrofuran,5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate and the saltsthereof, 2-chloro-3'-ethoxy-4'-nitro-4-trifluoromethyldiphenyl ether,1-(ethoxycarbonyl)ethyl5-(2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoate,5-(2-chloro-4-trifluoromethylphenoxy)-N-(methylsulfonyl)-2-nitrobenzamide,methyl 5-(2-chloro-4-trifluoromethylphenoxy)-2-nitroacetophenoneoxime-O-acetate, 3-amino-2-chloro-4-nitrodiphenyl ether and the like;

Triazine herbicides; 2-chloro-4-ethylamino-6-isopropylamino-1, 3,5-triazine, 2, 4-bis(ethylamino)-6-methylthio-1,3,5-triazine,2-ethylamino-4-(1,2-dimethylpropylamino)-6-methylthio-1,3,5-triazine,2,4-bis(isopropylamino)-6-methylthio-1,3,5-triazine,4-amino-6-t-butyl-3-methylthio-1,2,4-triazine-5(4H)-one,4-amino-6-t-butyl-3-ethylthio-1,2,4-triazine-5(4H)-one,2-chloro-4,6-bis(ethylamino)-1,3,5-triazine,2-(2-chloro-4-ethylamino-1,3,5-triazin-6-ylamino)-2-methylpropionitrileand the like;

Dinitroaniline herbicides;2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)aniline,N-(1-ethylpropyl)3,4-dimethyl-2,6-dinitroaniline, 3,5-dinitro-N⁴, N⁴-dipropylsulfanilide and the like;

Nitrile herbicides; 4-hydroxy-3,5-diiodobenzonitrile,3,5-dibromo-4-hydroxybenzonitrile, 2,6-dichlorobenzonitrile and thelike;

Phosphorous-containing herbicides; O-ethyl O-(5-methyl-2-nitrophenyl)N-sec-butylphosphoroamidate, S-(2-(benzenesulfonylamino)ethyl)O,O-diisopropyl phosphorodithioate,S-((2-methylpiperidin-1-yl)carbonylmethyl) O,O-dipropylphosphorodithioate, N-(phosphonomethyl)glycine, ammonium(DL-homoalanin-4-yl(methyl)phosphonate, sodium4-(hydroxy(methyl)phosphinoyy)-L-homoalanyl-L-alanyl-L-alanate, and thelike;

Quarternary-ammonium salts herbicides; 1,1'-ethylene-2,2'-bipyridiumdibromide, 1,1'-dimethyl-4,4'-bipyridium dichloride and the like;

Other herbicides; 3,6-dichloro-2-methoxybenzoate,3,7-dichloroquinoline-8-carboxylic acid, pentachlorophenol,2-sec-butyl-4,6-dinitrophenol, 2-amino-3-chloro-1,4-naphthoquinone,1,2-dihydropyridazine-3,6-dione, 3-(2methylphenoxy)pyridazine,3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide,2,2-dichloropropionic acid, 2,2,3,3-tetrafluoropropionic acid, methyl6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3(4)-methylbenzoate,2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid and thesalts thereof,2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylicacid, 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinicacid,1-methyl-4-(1-methylethyl)-2-((2-methylphenyl)methoxy)-7-oxabicyclo[2.2.1]heptane,1-(3-methylphenyl)-5-phenyl-1H-1,2,4-triazole-3-carboxamide,2-(N-ethoxybutylimidyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one,2-(3,5-dichlorophenyl)-2-(2,2,2-trichloroethyl)oxirane,N-[4-chlorobenzyloxy)phenyl]-3,4,5,6-tetrahydrophthalimide,N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-3,4,5,6-tetrahydrophthalimide,3-(2,4-dichloro-5-isopropoxyphenyl)-5-t-butyl-1,3,4-oxadiazole-2(3H)-one,4-methoxy-3,3'-dimethylbenzophenone,2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl methanesulfonate,1-methyl-3-phenyl-5-(3-trifluoromethylphenyl)pyridine-4(1H)-one,2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone, (E),(E)-2-(1-(3-chloropropen-2-yloxyimino)butyl)-5-(2-ethylthiopropyl)-3-hydroxy-2-cyclohexen-1-one,2-(1-ethoxyiminopropyl)-3-hydroxy-5-dimethyl-2-dichlorohexen-1-one andthe like.

These can be mixed in plurality for use.

The present invention will now be explained in details with referencewith examples, but the invention is not limited to the followingexamples, unless departing from the scope thereof.

Example 1N-(3-(4-Acetoxytetrahydrofuran-3-yloxycarbonyl)-4-chlorophenyl)-3,4,5,6-tetrahydrophthalimide

A mixture of 12.2 g ofN-(3-carboxy-4-chlorophenyl)-3,4,5,6-tetrahydrophthalimide and 20 ml ofthionyl chloride was refluxed under stirring for 2 hours. Distilling offexcess thionyl chloride, the resulting acid chloride was dissolved in 40ml of ethyl acetate. In 80 ml of ethyl acetate were dissolved 6.4 g of3-acetoxy-4-hydroxytetrahydrofuran and 4.9 g of triethylamine, to whichwas added a solution of the acid chloride in ethyl acetate understirring. After stirring at room temperature for 3 hours, the reactionmixture was washed with water and subsequently with aqueous saturatedsodium chloride solution, and dried over anhydrous magnesium sulfate.After distilling off the solvent, the residue was purified bychromatography on a silica gel column (eluted with ethyl acetate/hexane=1/2), to obtain 11.7 g of a compound described in Table 1 (No. 1)(67%).

Example 2N-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenyl)-3,4,5,6-tetrahydrophthalimide

In 15 ml of benzene were dissolved 0.66 g ofN-(4-chloro-2-fluoro-5-(4-hydroxytetrahydrofuran-3-yloxycarbonylmethoxy)phenyl)-3,4,5,6tetrahydrophthalimideand 0.20 g of triethylamine, followed by dropwise addition of a solutionof 0.14 g of acetyl chloride in benzene. After stirring at roomtemperature for 4 hours, the reaction mixture was washed with water andsubsequently with aqueous saturated sodium chloride solution, and 'driedover anhydrous magnesium sulfate. After distilling off the solvent, theresidue was purified by chromatography on a silica gel column (elutedwith ethyl acetate/hexane=2/3), to obtain 0.55 g of a compound describedin Table 1 (No.3) (76%).

Example 39-(4-Chloro-5-(4-(chloroacetoxy)tetrahydrofuran-3-yloxycarbonylmethylthio)-2-fluorophenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one

In 25 ml of dichloromethane were dissolved 1.19 g of9-(4-chloro-2-fluoro-5-(4-hydroxytetrahydrofuran-3-yloxycarbonylmethylthio)phenylimino)-8-thia-1,6diazabicyclo[4.3.0]nonan-7-one and 0.24 g of pyridine,followed by dropwise addition of a solution of 0.34 g of chloroacetylchloride in dichloromethane. After stirring at room temperatureovernight, the reaction mixture was washed with water, and subsequentlywith aqueous saturated sodium chloride solution, and dried overanhydrous magnesium sulfate. After distilling off the solvent, theresidue was purified by chromatography on a silica gel column (elutedwith ethyl acetate/hexane =2/3), to obtain 1.02 g of a compounddescribed in Table 1 (No. 32) (74%).

Example 49-(4-Chloro-2-fluoro-5-(4-methylsulfonyloxy)tetrahydrofuran-3-yloxycarbonylmethylthio)phenylimino-8-thia-1,6diazabicyclo[4.3.0]nonan-7-one

In 15 ml of pyridine was dissolved 1.43 g of9-(4-chloro-2-fluoro-5-(4-hydroxytetrahydrofuran-3-yloxycarbonylmethylthio)phenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one,followed by dropwise addition of 0.69 g of methanesulfonyl chlorideunder stirring while in ice cooling and subsequent stirring overnight atroom temperature. After distilling off pyridine under reduced pressure,the residue was extracted with toluene, which was then washedsequentially with water, dilute hydrochloric acid, aqueous saturatedsodium hydrogencarbonate solution, and aqueous saturated sodium chloridesolution, and dried over anhydrous magnesium sulfate. After distillingoff the solvent, the residue was purified by chromatography on a silicagel column (eluted with ethyl acetate/hexane =3/2), to obtain 1.40 g ofa compound described in Table 1 (No. 25) (84%).

Example 59-(4-Chloro-5-(4-(ethoxycarbonyloxy)tetrahydrofuran-3-yloxycarbonylmethylthio)-2-fluorophenylimino-8-thia-1,6diazabicyclo[4.3.0]nonan-7-one

In 15 ml of pyridine was dissolved 1.43 g of9-(4-chloro-2-fluoro-5-(4-hydroxytetrahydrofuran-3-yloxycarbonylmethylthio)phenylimino)-8-thia-1,6diazabicyclo[4.3.0]nonan-7-one,followed by dropwise addition of 0.65 g of ethyl chloroformate understirring while in ice cooling and subsequent stirring overnight at roomtemperature. After distilling off pyridine under reduced pressure, theresidue was extracted with ethyl acetate, which was then washed withwater and subsequently with aqueous saturated sodium chloride solution,and dried over anhydrous magnesium sulfate. After distilling off thesolvent, the residue was purified by chromatography on a silica gelcolumn (eluted with ethyl acetate/hexane=2/3), to obtain 1.38 g of acompound described in Table 1 (No. 36) (84%).

Example 6N-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethylthio)-4-chloro-2-fluorophenyl)3,4,5,6-tetrahydrophthalimide

A mixture of 14.0 g ofN-(4-chloro-2-fluoro-5-mercaptophenyl)-3,4,5,6-tetrahydrophthalimide,11.0 g of 4-acetoxytetrahydrofuran-3-yl chloroacetate, 7.46 g ofpotassium carbonate, 1.5 g of potassium iodide and 150 ml of acetone wasrefluxed under stirring for 5 hours. After cooling, the salt wasfiltered off, and the residue was purified by chromatography on a silicagel column (eluted with ethyl acetate/hexane=2/3), to obtain 14.5 g of acompound described in Table 1 (No. 6) (65%).

Example 7N-(5-(1-(4-Acetoxytetrahydrofuran-3-yloxycarbonyl)ethylamino)-4-chloro-2-fluorophenyl)-3,4,5,6-tetrahydrophthalimide

A mixture of 8.84 g ofN-(5-amino-4-chloro-2-fluorophenyl)-3,4,5,6-tetrahydrophthalimide, 12.6g of 4-acetoxytetrahydrofuran-3-yl 2-bromopropionate, 3.02 g of sodiumhydrogencarbonate and 3 ml of xylene was heated under stirring at 150°to 160 ° C. for 4 hours. Adding ethyl acetate to the reaction mixturewhile it remained warm, the resulting mixture was washed with water,subsequently with aqueous saturated sodium chloride solution, and driedover anhydrous magnesium sulfate. After distilling off the solvent, theresidue was purified by chromatography on a silica gel column(development solvent: ethyl acetate/hexane=1/2), to obtain 4.88 g of acompound described in Table 1 (No. 10) (33%).

Example 81-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenylaminothiocarbonyl)-2-(ethoxycarbonyl)hexahydroxypridazine

Seventy-five milliliters of water were cooled in an ice-cold bath,followed by addition of 2.3 g of thiophosgene and subsequent dropwiseaddition of a solution of 5.2 g of5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluoroanilinein 150 ml of chloroform. After stirring at room temperature for 2 hours,the organic layer was washed with water, subsequently with aqueoussaturated sodium chloride solution, and dried over anhydrous magnesiumsulfate. After distilling off the solvent, the resulting isothiocyanatewas dissolved in 75 ml of benzene, followed by addition of 2.4 g ofethyl 1,2-tetramethylenecarbazate, which was then refluxed understirring for 1 hour. After cooling, the reaction mixture was washed withwater, subsequently with aqueous saturated sodium chloride solution, anddried over anhydrous magnesium sulfate. After distilling off thesolvent, the residue was purified by chromatography on a silica gelcolumn (eluted with ethyl acetate/chloroform =1/6), to obtain 5.3 g of acompound (No. 17) described in Table 1 (64%).

Example 94-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenyl)1,2-tetramethylene-3-thiourazole

In 20 ml of toluene were dissolved 2.19 g of1-(5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenylaminothiocarbonyl)-2-(ethoxycarbonyl)hexahydropyridazineand 0.49 g of triethylamine, and refluxed under stirring for 8 hours.After distilling off the solvent from the reaction mixture, the residuewas purified by chromatography on a silica gel column (eluted with ethylacetate/hexane=3/2), to obtain 1.34 g of a compound (No. 14) describedin Table 1 (67%).

Example 103-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenyl)-1,5-tetramethylene-2-thiohydantoin

A mixture of the isothiocyanate produced from 1.39 g of5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluoroanilinein the same fashion as in Example 8, 0.62 g of pipecolic acid and 20 mlof ethanol was refluxed under stirring for 4 hours. To the resultingmixture was poured water, which was then extracted with ethyl acetate,washed with aqueous saturated sodium chloride solution, and dried overanhydrous magnesium sulfate. After distilling off the solvent, theresidue was purified by chromatography on a silica gel column (elutedwith ethyl acetate/hexane =1/1), to obtain 1.05 g of a compound (No. 12)described in Table 1 (52%).

Example 119-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethylthio)-4-chloro-2-fluorophenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one

In 15 ml of dichloromethane was dissolved 1.48 g of1-(5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethylthio)-4-chloro-2-fluorophenylaminothiocarbonyl)hexahydropyridazine,followed by addition of 0.59 g of pyridine, which was then cooled in anice-cold bath. Under stirring, 3.3 g of a 26.8% solution of phosgene intoluene was added dropwise, and after addition was completed, theresulting product was stirred at room temperature for 3 hours. Thereaction mixture was washed with water, subsequently with aqueoussaturated sodium chloride solution, and dried over magnesium sulfate.After distilling off the solvent, the residue was purified bychromatography on a silica gel column (eluted with ethylacetate/hexane=1/1), to obtain 1.20 g of a compound (No. 26) describedin Table 1 (77%).

Example 129-(5-(4-Acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenylimino)-8-thia-1,6diazabicyclo[4.3.0]nonan-7-thione

In 15 ml of dichloromethane was dissolved 1.43 g of1-(5-(4-acetoxytetrahydrofuran-3-yloxycarbonylmethoxy)-4-chloro-2-fluorophenylaminothiocarbonyl)hexahydropyridazine,followed by addition of 0.59 g of pyridine, which was then cooled in anice-cold bath. Under stirring, a solution of 0.52 g of thiophosgene indichloromethane was added dropwise, and after addition was completed,the resulting mixture was stirred at room temperature for 3 hours. Thereaction mixture was washed with water, subsequently with aqueoussaturated sodium chloride solution, and dried over magnesium sulfate.After distilling off the solvent the residue was purified bychromatography on a silica gel column (eluted with ethylacetate/hexane=2/3), to obtain 1.12 g of a compound (No. 42) describedin Table 1 (72%).

The other compounds described in Table 1 can be synthesized according toany of the methods described in the Examples 1 to 12. All of thestructures of the resulting compounds were confirmed by IR, NMR spectraand the like. The physical properties and ¹ H-NMR spectra of thecompounds described in Table 1 are shown in Table 2.

                                      TABLE 1                                     __________________________________________________________________________    Compoiund                                 Synthesis                           No.   Z           X  Y  A      R          (Example No.)                       __________________________________________________________________________     1                                                                                   ##STR21##  Cl H  Direct bonding                                                                        ##STR22## 1                                    2    "           Cl F  OCH.sub.2                                                                            OH         6                                    3    "           Cl F  OCH.sub.2                                                                             ##STR23## 2                                    4    "           Cl F  SCH.sub.2                                                                            H          6                                    5    "           Cl F  SCH.sub.2                                                                            OH         "                                    6    "           Cl F  SCH.sub.2                                                                             ##STR24## "                                    7    "           Cl F                                                                                 ##STR25##                                                                            ##STR26## "                                    8    "           Cl F                                                                                 ##STR27##                                                                            ##STR28## "                                    9    "           Cl F  NHCH.sub.2                                                                            ##STR29## 7                                   10    "           Cl F                                                                                 ##STR30##                                                                            ##STR31## "                                   11                                                                                   ##STR32##  Cl F  NHCH.sub.2                                                                            ##STR33## 7                                   12                                                                                   ##STR34##  Cl F  OCH.sub.2                                                                             ##STR35## 10                                  13                                                                                   ##STR36##  Cl H  Direct bonding                                                                        ##STR37## 9                                   14    "           Cl F  OCH.sub.2                                                                             ##STR38## "                                   15    "           Cl F  SCH.sub.2                                                                             ##STR39## 9                                   16                                                                                   ##STR40##  Cl H  Direct bonding                                                                        ##STR41## 8                                   17    "           Cl F  OCH.sub.2                                                                             ##STR42## "                                   18                                                                                   ##STR43##  Cl H  Direct bonding                                                                        ##STR44## 11                                  19    "           Cl H  SCH.sub. 2                                                                            ##STR45## "                                   20    "           Cl F  OCH.sub.2                                                                            OH         "                                   21    "           Cl F  OCH.sub.2                                                                             ##STR46## "                                   22    "           Cl F  SCH .sub.2                                                                           H          "                                   23    "           Cl F  SCH .sub.2                                                                           OH         "                                   24    "           Cl F  SCH.sub.2                                                                             ##STR47## "                                   25    "           Cl F  SCH.sub.2                                                                            OSO.sub.2 CH.sub.3                                                                       4                                   26    "           Cl F  SCH.sub.2                                                                             ##STR48## 11                                  27    "           Cl F  SCH.sub.2                                                                             ##STR49## "                                   28                                                                                   ##STR50##  Cl F  SCH.sub.2                                                                             ##STR51## 11                                  29    "           Cl F  SCH.sub.2                                                                             ##STR52## "                                   30    "           Cl F  SCH.sub.2                                                                             ##STR53## "                                   31    "           Cl F  SCH.sub.2                                                                             ##STR54## "                                   32    "           Cl F  SCH.sub.2                                                                             ##STR55## 3                                   33    "           Cl F  SCH.sub.2                                                                             ##STR56## 11                                  34    "           Cl F  SCH.sub.2                                                                             ##STR57## 3                                   35    "           Cl F  SCH.sub.2                                                                             ##STR58## "                                   36    "           Cl F  SCH.sub.2                                                                             ##STR59## 5                                   37    "           Cl F                                                                                 ##STR60##                                                                            ##STR61## 11                                  38                                                                                   ##STR62##  Cl F                                                                                 ##STR63##                                                                            ##STR64## 11                                  39    "           Cl F  NHCH.sub.2                                                                            ##STR65## "                                   40    "           Cl F                                                                                 ##STR66##                                                                            ##STR67## "                                   41    "           Cl Cl SCH.sub.2                                                                             ##STR68## "                                   42                                                                                   ##STR69##  Cl F  OCH.sub.2                                                                             ##STR70## 12                                  43    "           Cl F  SCH.sub.2                                                                             ##STR71## "                                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________          Melting point                                                           Compound                                                                            or refractive                                                           No.   index  .sup.1 H-NMR (δ, CDCl.sub.3)                               __________________________________________________________________________     1           7.93(1H,d), 7.57-7.48(2H, m), 5.58(1H, q), 5.44(1H, q),                       4.23-4.12(2H, m),                                                             4.01(1H, dd), 3.86(1H, dd), 2.47-2.40(4H, m), 2.09(3H, s),                    1.87-1.80(4H, m)                                                  2    mp     7.27(1H, d), 6.80(1H, d), 5.11(1H, q), 4.72(2H, s), 4.34(1H,                  q), 4.09-3.34                                                          111˜113.5° C.                                                           (4H, m), 2.69(1H, d), 2.39(4H, m), 1.81(4H, m)                    3           7.32(1H, d), 6.86(1H, d), 5.41(2H, m), 4.70(2H, s)                            4.19-3.70(4H, m), 2.04                                                        (3H, s), 2.44(4H, m), 1.83(4H, m)                                 4    mp     7.40(1H, d), 7.33(1H, d), 5.32-5.27(1H, m), 3.88-3.73(4H,                     m), 3.64(2H, s),                                                       116˜117° C.                                                             2.47-2.40(4H, m), 2.21-2.08(1H, m), 1.98-1.88(1H, m),                         1.87-1.79(4H, m)                                                  5    mp     7.41(1H, d), 7.33(1H, d), 5.14(1H, q), 4.44(1H, q). 4.03(1H,                  dd), 3.93(1H, dd),                                                     153˜154° C.                                                             3.78(1H, dd), 3.72(2H, AB), 3.59(1H, dd), 2.47-2.38(4H, m),                   1.87-1.78(4H, m)                                                  6           7.41(1H, d), 7.33(1H, d), 5.37-5.27(2H, m), 4.06-4.00(2H,                     m), 3.79-3.72                                                                 (2H, m), 3.67(2H, s), 2.47-2.40(4H, m), 2.04(3H, s),                          1.86-1.79(4H, m)                                                  7           7.49, 7.48(Total 1H, d), 7.36, 7.34(Total 1H, d),                             5.33-5.25(2H, m), 4.10-3.87(3H, m),                                           3.79-3.58(2H, m), 2.47-2.40(4H, m), 2.05, 2.04(Total 3H, s),                  1.87-1.80(4H, s),                                                             1.54(3H, d)                                                       8           7.48(1H, d), 7.35, 7.33(Total 1H, d), 5.33-5.25(2H, m),                       4.10-3.74(2H, m), 3.78-                                                       3.55(3H, m), 2.47-2.40(4H, m), 2.04, 2.03(Total 3H, s),                       2.02-1.79(6H, m), 1.08,                                                       1.08(Total 3H, t)                                                 9           7.22(1H, d), 6.38(1H,d), 5.45(1H, q), 5.33(1H, q), 4.84(1H,                   bd), 4.13-4.06                                                                (2H, m), 3.96(2H, s), 3.88-3.77(2H, m), 2.46-2.39(4H, m),                     2.04(3H, s), 1.86-                                                            1.79(4H, m)                                                      10           7.21(1H, d), 6.42, 6.41(Total 1H, d), 5.45-5.28(2H, m),                       4.73, 4.65(Total 1H, bd), 4.20-                                               4.02(3H, m), 3.90-3.71(2H, m), 2.46-2.39(4H, m), 2.01,                        1.97(Total 3H, s), 1.85-                                                      1.79(4H, m), 1.54(3H, d)                                         11           7.23(1H, d), 6.44(1H, d), 5.46(1H, q), 5.34(1H, q), 4.86(1H,                  bs), 4.28-3.78                                                                (8H, m), 2.98-2.87(1H, m), 2.34-2.26(1H, m), 2.10-2.02(1H,                    m), 2.05(3H, s)                                                               1.84-1.76(1H, m), 1.62-1.41(3H, m)                               12           7.32, 7.32(Total 1H, d) 6.95-6.87(1H, m), 5.49-5.41(1H, m),                   5.37-5.30(1H, m)                                                              4.92-4.84(1H, m), 4.78-4.63(2H, m), 4.14-4.00(3H, m),                         3.88-3.77(2H, m),                                                             3.16-3.04(1H, m), 2.38-2.30(1H, m) 2.14-2.04(1H, m) 2.07,                     2.06, 2.05, 2.05                                                              (Total 3H, s), 1.96-1.84(1H, m), 1.72-1.48(3H, m)                13    mp     8.04-8.02(1H, m), 7.62-7.60(2H, m), 5.61-5.56(1H, m),                         5.44(1H, q), 4.22-                                                     157.5˜158.5° C.                                                         3.99(5H, m), 3.86(1H, dd), 3.77-3.70(2H, m), 2.07(3H, s),                     2.06-1.94(4H, m)                                                 14           7.35(1H, d), 6.98(1H, d), 5.45(1H, q), 5.33(1H, q), 4.71(2H,                  AB), 4.12-3.99                                                                (4H, m), 3.88-3.68(4H, m), 2.06(3H, s), 2.04-1.94(4H, m)         15           7.57, 7.55(Total 1H, d), 7.37(1H, d), 5.37-5.27(2H, m),                       4.14-3.93(4H, m), 3.83-                                                       3.64(6H, m), 2.06, 2.05(Total 3H, s), 2.05-1.93(4H, m)           16           8.38(1H, bs), 7.95-7.93(1H, m), 7.72(1H, dd), 7.45(1H, d),                    5.60-5.40(3H, m),                                                             4.34-3.84(7H, m), 3.14-3.00(2H, m), 2.07(3H, s),                              1.94-1.70(4H, m), 1.33                                                        (3H, t)                                                          17           8.46, 8.45(Total 1H, bs), 8.18, 8.15(Total 1H, d), 7.17(1H,                   d), 5.50-5.42(2H, m), 5.33                                                    (1H, q), 4.75(2H, s), 4.33-4.06(5H, m), 3.92-3.77(2H, m),                     3.11-2.99(2H, m),                                                             2.08, 2.07(Total 3H, s), 1.90-1.70(4H, m), 1.30(3H, t)           18           7.43(1H, d), 7.41(1H, d), 7.03(1H, dd), 5.60-5.54(1H, m),                     5.44(1H, q), 4.23-                                                            4.11(2H, m), 4.01(1H, dd), 3.87(1H, dd), 3.80-3.71(4H, m),                    2.05(3H, s), 1.98-                                                            1.79(4H, m)                                                      19    mp     7.32(1H, d), 6.98(1H, d), 6.75(1H, dd), 5.39-5.27(2H, m),                     4.09-4.03(2H, m),                                                      130.5-131.5° C.                                                               3.84-3.70(6H, m), 3.71(2H, s), 2.02(3H, s), 1.96-1.78(4H,                     m)                                                               20    mp     7.18(1H, d), 6.55(1H, d), 5.28-5.23(1H, m), 4.74(2H, s),                      4.54-4.46(1H, m),                                                      139˜140.5° C.                                                           4.09(1H, dd), 3.99(1H, dd), 3.87(1H, dd), 3.81-3.64(5H, m),                   2.17(1H, bd),                                                                 1.97-1.78(4H, m)                                                 21           7.18(1H, d), 6.54(1H, d), 5.46(1H, q), 5.33(1H, q), 4.67(2H,                  AB), 4.13-4.05                                                                (2H, m), 3.88-3.71(6H, m), 2.06(3H, s), 1.97-1.78(4H, m)         22    mp     7.20(1H, d), 7.11(1H, d), 5.33-5.28(1H, m), 3.92-3.71(8H,                     m), 3.62(2H, s),                                                        92˜94° C.                                                              2.22-2.09(1H, m), 2.00-1.79(5H, m)                               23           7.21(1H, d), 7.12(1H, d), 5.18-5.12(1H, m), 4.48-4.41(1H,                     m), 4.04(1H, dd),                                                             3.96(1H, dd), 3.82-3.64(6H, m), 3.71(2H, s), 2.18(1H, bs),                    1.97-1.79(4H, m)                                                 24           7.37-7.25(5H, m), 7.17(1H, d), 7.10(1H, d), 5.35-5.30(1H,                     m), 4.52(2H, AB),                                                             4.18-3.67(9H, m), 3.69(2H, AB), 1.93-1.75(4H, m)                 25           7.20(1H, d), 7.12(1H, d), 5.30(1H, q), 5.22-5.17(1H, m),                      4.13-3.95(3H, m),                                                             3.83-3.70(5H, m), 3.71(2H, s), 3.05(3H, s), 1.97-1.79(4H,                     m)                                                               26    mp     7.20(1H, d), 7.12(1H, d), 5.37-5.27(2H, m), 4.09-4.02(2H,                     m), 3.83-3.72                                                          106.5˜108° C.                                                           (2H, m), 3.65(2H, s), 2.04(3H, s), 1.97-1.79(4H, m)              27           7.20(1H, d), 7.12(1H, d), 5.38-5.28(2H, m), 4.10-4.02(2H,                     m), 3.83-3.71                                                                 (6H, m), 3.64(2H, s), 2.32(2H, q), 1.98-1.79(4H, m),                          1.12(3H, t)                                                      28           7.20(1H, d), 7.12(1H, d), 5.38-5.28(2H, m), 4.10-4.02(2H,                     m), 3.82-3.72                                                                 (6H, m), 3.64(2H, s), 2.27(2H, t), 1.97-1.79(4H, m),                          1.69-1.56(2H, m),                                                             0.93(3H, t)                                                      29    nd 23.0° C.                                                                   7.20(1H, d), 7.12(1H, d), 5.38-5.26(2H, m), 4.11-4.03(2H,                     m), 3.82-3.71                                                          1.5899 (6H, m), 3.63(2H, AB), 2.54(1H, sep), 1.97-1.79(4H, m),                       1.16(3H, d),                                                                  1.15(3H, d)                                                      30           7.20(1H, d), 7.12(1H, d), 5.37-5.28(2H, m), 4.10-4.02(2H,                     m), 3.82-3.7                                                                  (6H, m), 3.64(2H, s), 2.29(2H, t), 1.97-1.79(4H, m),                          1.63-1.53(2H, m),                                                             1.39-1.27(2H, m), 0.90(3H, t)                                    31           7.20(1H, d), 7.12(1H, d), 5.37-5.28(2H, m), 4.10-4.02(2H,                     m), 3.82-3.71                                                                 (6H, m), 3.63(2H, s), 2.19-2.16(2H, m), 2.13-2.00(1H, m),                     1.97-1.79                                                                     (4H, m), 0.94(6H, d)                                             32           7.21(1H, d), 7.11(1H, d), 5.43-5.33(2H, m), 4.12-4.04(2H,                     m), 4.07(2H, AB),                                                             3.86-3.72(6H, m), 3.65(2H, s), 1.97-1.79(4H, m)                  33    nd 23.5° C.                                                                   7.20(1H, d), 7.11(1H, d), 5.96-5.81(1H, m), 5.38-5.29(2H,                     m), 5.22-5.13                                                          1.5994 (2H, m), 4.10-4.02(2H, m), 3.83-3.71(6H, m), 3.09(2H, d),                     1.98-1.79(4H, m)                                                 34           7.20(1H, d), 7.12(1H, d), 5.37-5.26(2H, m), 4.10-4.02(2H,                     m), 3.82-3.72                                                                 (6H, m), 3.63(2H, s), 2.35-2.24(1H, m), 1.97-1.57(9H, m),                     1.48-1.16(5H, m)                                                 35           8.02-7.98(2H, m), 7.61-7.55(1H, m), 7.47-7.40(2H, m),                         7.10(1H, d), 7.06                                                             (1H, d), 5.56-5.44(2H, m), 4.24-4.10(2H, m), 3.98-3.70(6H,                    m), 3.59(2H, s),                                                              1.96-1.78(4H, m)                                                 36           7.20(1H, d), 7.13(1H, d), 5.34(1H, q), 5.21(1H, q), 4.20(2H,                  q), 4.12-4.04                                                                 (2H, m), 3.89-3.82(6H, m), 3.65(2H, AB), 1.97-1.79(4H, m),                    1.31(3H, t)                                                      37           7.24-7.18(2H, m), 5.34-5.25(2H, m), 4.10-3.96(2H, m),                         3.90-3.63(7H, m),                                                             2.06, 2.05(Total 3H, s), 1.52, 1.51(Total 3H, d)                 38           7.23-7.17(2H, m), 5.34-5.25(2H, m), 4.11-3.97(2H, m),                         3.83-3.61(7H, m),                                                             2.04, 2.04(Total 3H, s), 2.01-1.78(6H, m), 1.07, 1.07(Total                   3H, t)                                                           39           7.10(1H, d), 6.13(1H, d), 5.44(1H, q), 5.34(1H, q), 4.74(1H,                  bs), 4.13-4.06                                                                (2H, m), 3.95(2H, bs), 3.88-3.70(6H, m), 2.05(3H, s),                         1.97-1.78(4H, m)                                                 40           7.09(1H, d), 6.18, 6.15(Total 1H, d), 5.44-5.28(2H, m),                       4.63, 4.55(Total 1H, bd),                                                     4.17-4.04(3H, m), 3.90-3.70(6H, m), 2.03, 1.99(Total 3H, s),                  1.97-1.77(4H, m),                                                             1.54(3H, d)                                                      41           7.45(1H, s), 7.00(1H, s), 5.38-5.27(2H, m), 4.09-4.02(2H,                     m), 3.84-3.72                                                                 (6H, m), 3.68(2H, s), 2.03(3H, s), 1.98-1.79(4H, m)              42           7.18(1H, d), 6.52(1H, d), 5.47(1H, q), 5.34(1H, q), 4.67(2H,                  AB), 4.20-4.05                                                                (4H, m), 3.90-3.78(4H, m), 2.06(3H, s), 2.04-1.90(4H, m)         43           7.20(1H, d), 7.10(1H, d), 5.39-5.28(2H, m), 4.21-4.15(2H,                     m), 4.09-4.03                                                                 (2H, m), 3.92-3.86(2H, m), 3.83-3.76(2H, m), 3.65(2H, s),                     2.05(3H, s),                                                                  2.04-1.92(4H, m)                                                 __________________________________________________________________________

The formulation examples of the compound of the present invention willnow be shown hereinbelow. By the terms "part" and "%" are meant "part byweight" and "% by weight," respectively.

Formulation Example 1: Wettable powder

Forty parts of a compound of the present invention shown in Table 1, 20parts of Carplex #80 (as registered trade mark; manufactured by Shionogi& Co., Ltd.), 35 parts of N,N Kaolin Clay (as registered trade mark;manufactured by Tuchiya Kaolin Co., Ltd.), and 5 parts of a higheralcohol sulfate surfactant sorpol 8070 (as registered trade mark;manufactured by TOHO CHEMICAL INDUSTRY COMPANY, LIMITED) were compoundedtogether, and subsequently mixed together and ground homogeneously, toobtain a wettable powder containing the active ingredient at 40%.

Formulation Example 2: Emulsifiable concentrate

Twenty parts of a compound of the present invention shown in Table 1were dissolved in a mixture solvent composed of 35 parts of xylene and30 parts dimethylformamide, to which was then added 15 parts of apolyoxyethylene surfactant Sorpol 3005X (as registered trade mark;manufactured by TOHO CHEMICAL INDUSTRY COMPANY, LIMITED), to obtain anemulsifiable concentration containing the active ingredient at 20%.

Formulation Example 3: Flowable

Thirty parts of a compound of the present invention shown in Table 1 wasthoroughly mixed and dispersed in preliminarily mixed 8 parts ofethylene glycol, 5 parts of Sorpol AC 3020 (as registered trade mark;manufactured by TOHO CHEMICAL INDUSTRY COMPANY, LIMITED), 0.1 part ofxanthan gum and 56.9 parts of water, and the resulting slurry mixturewas subsequently wet ground with a Dynomill (as registered trade mark;manufactured by Shinmaru Enterprises Corporation), to obtain a stableflowable containing the active ingredient at 30%.

Formulation Example 4: Granule

One part of a compound of the present invention shown in Table 1, 43parts of clay (manufactured by Nippon Talc Kabushiki Kaisha), 55 partsof bentonite (manufactured by Hojun Yoko Kabushiki Kaisha), and one partof a succinate surfactant Airroll CT-1 (as registered trade mark;manufactured by TOHO CHEMICAL INDUSTRY COMPANY, LIMITED) were blendedtogether, and mixed together and ground, followed by addition of water.The resulting mixture was then kneaded.

By using an extrusion granulating machine, the resulting mixture wasextruded from holes each of a diameter of 0.6 mm, and dried at 60 ° C.for 2 hours, which was then cut at a length of 1-2 mm, to obtain agranule containing the active ingredient at 1%.

The test examples of the compound of the present invention will now beshown below.

The Comparative Compounds (A) to (E) in the Test Examples herein showthe following compounds. Comparative Compound (A)

Acifluorfen-sodium ##STR72##

Comparative Compound (B)

9-(4-Chloro-2-fluoro-5-(isopropyloxy)phenylimino)-8-thia-1,6diazabicyclo[4.3.0]nonan-7-one(disclosed in Japanese Patent Laid-open No. 91/1987) ##STR73##

Comparative Compound (C)

9-(5-(n-Butoxycarbonylmethylthio)-4-chloro-2-fluorophenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one(disclosed in European Patent Publication No. 273417) ##STR74##

Comparative Compound (D)

9-(4-Chloro-5(cyclopentyloxycarbonylmethylthio ) -2-fluorophenylimino8-thia-1,6-diazabicyclo[4.3.0]nonan-7-on (disclosed in European PatentPublication No. 273417) ##STR75##

Comparative Compound (E)

9-(4-Chloro-2-fluoro-5(tetrahydrofuran-2-ylmethoxycarbonylmethylthio)phenylimino)-8-thia-1,6-diazabicyclo[4.3.0]nonan-7-one (disclosed in Japanese Patent Laid-open No. 199978/1991)##STR76##

Test Example 1: Foliar application test

A small, styrol foaming-made pot of an area of 110 cm² was filled withandosol of volcanic ash, followed by application of a fertilizer. Then,each seed of Amaranthus viridis, Polygonum lapathifolium, Abutilontheophrasti, Xanthium strumarium, Galium aparine, Viola tricolor, corn,wheat and soybean was seeded in an individual pot.

The culture control was continued in a greenhouse. Dilution of thewettable powder containing as the active ingredient the compound of thepresent invention obtained by the Formulation Example 1, and thewettable powder individually containing as the effective ingredients theComparative Compounds (A), (B), and (C) obtained in the same fashion asin the Formulation Example 1 were done separately with water so that theactive ingredient contents might be 250,125, 63 and 32 g/ha. An amountof 500 liters as the application solution volume per 1 ha was applied tothe foliage parts with small power pressure sprayers when Amaranthusviridis seedlings reached 3.5 leaf stage; Polygonum lapathifolium, 3leaf stage; Abutilon theophrasti seedlings, 3 leaf stage; Xanthiumstrumarium seedlings, 3 leaf stage; Galium aparine seedlings, 2node-leaf stage; Viola tricolor seedlings, 3 leaf stage; corn seedlings,3.5 leaf stage; wheat seedlings, 2.5 leaf stage; and soybean seedlings,1.5 leaf stage.

Subsequently, the culture control was continued in the greenhouse, andon day 21 after the chemical application, observation was done aboutherbicidal effect and crop injury.

The results are shown in Table 3.

The assessment of herbicidal effect was done as follows:

The value; ##EQU1## was determined, which was then represented as theherbicidal effect coefficient according to the following criteria:

    ______________________________________                                        Herbicidal effect                                                             coefficient      Y (%)                                                        ______________________________________                                        0                0-5                                                          1                 6-30                                                        2                31-50                                                        3                51-70                                                        4                71-90                                                        5                 90-100                                                      ______________________________________                                    

The assessment of crop injury was done as follows:

The value; ##EQU2## was determined, which was then represented as thecrop injury coefficient according to the following criteria:

    ______________________________________                                               Crop injury                                                                   coefficient                                                                           Y (%)                                                          ______________________________________                                               0       0-5                                                                   1        6-10                                                                 2       11-20                                                                 3       21-40                                                                 4       41-60                                                                 5        61-100                                                        ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________           Rate of                                                                             Herbicidal effect                                                Compound                                                                             application                                                                         Amaranthus                                                                           Polygonum                                                                            Abutilon                                                                            Xanthium                                                                             Galium                                                                             Viola                                                                              Crop injury                 No.    g/ha  viridis                                                                              lapathifolium                                                                        theophrasti                                                                         strumarium                                                                           aparine                                                                            tricolor                                                                           corn                                                                              wheat                                                                             soybean             __________________________________________________________________________     2     250   5      5      5     5      5    5    0   0   1                          125   5      4      5     3      5    5    0   0   0                    4     250   5      5      5     5      5    5    0   0   0                          125   5      5      5     4      5    5    0   0   0                    5     250   5      5      5     5      5    5    0   0   0                          125   5      5      5     3      4    5    0   0   0                    6     250   5      5      5     5      5    5    0   0   0                          125   5      5      4     4      5    5    0   0   0                    7     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                    8     63    5      5      5     5      5    5    0   0   0                          32    5      5      5     5      5    5    0   0   0                    9     63    5      5      5     5      5    5    0   1   1                          32    5      5      5     5      5    5    0   0   0                   10     63    5      5      5     5      5    5    1   1   1                          32    5      5      5     5      5    5    0   0   1                   11     125   5      5      5     5      5    5    0   1   1                          63    5      5      5     3      4    5    0   0   0                   12     125   5      5      5     5      5    5    0   0   0                          63    5      4      5     3      4    4    0   0   0                   13     125   5      5      5     5      5    5    0   0   1                          63    5      5      5     3      4    5    0   0   0                   14     125   5      5      5     5      5    5    0   0   0                          63    5      4      5     4      4    5    0   0   0                   18     125   5      5      5     5      5    5    0   0   1                          63    5      5      5     4      5    5    0   0   0                   20     125   5      5      5     5      5    5    0   1   1                          63    5      5      5     4      5    5    0   0   0                   21     125   5      5      5     5      5    5    0   0   1                          63    5      5      5     4      5    5    0   0   0                   22     63    5      5      5     5      5    5    0   1   2                          32    5      5      5     5      5    5    0   0   0                   23     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   25     63    5      5      5     5      5    5    0   1   1                          32    5      5      5     5      5    5    0   0   0                   26     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   27     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   28     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   29     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   30     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   31     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   33     63    5      5      5     5      5    5    0   0   0                          32    5      5      5     5      5    5    0   0   0                   34     63    5      5      5     5      5    5    0   1   1                          32    5      5      5     5      5    5    0   0   0                   35     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   36     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   37     63    5      5      5     5      5    5    0   0   1                          32    5      5      5     5      5    5    0   0   0                   38     63    5      5      5     5      5    5    0   1   1                          32    5      5      5     5      5    5    0   0   0                   39     63    5      5      5     5      5    5    1   1   0                          32    5      5      5     5      5    5    0   0   0                   40     63    5      5      5     5      5    5    0   1   1                          32    5      5      5     5      5    5    0   0   0                   42     125   5      5      5     5      5    5    0   0   1                          63    5      5      5     4      5    5    0   0   0                   43     125   5      5      5     5      5    5    0   0   0                          63    5      5      5     5      5    5    0   0   0                   Comparative                                                                          250   5      5      3     4      3    4    1   2   1                   compound                                                                             125   2      3      2     2      1    1    0   0   0                   (A)                                                                           Comparative                                                                          125   5      5      5     4      5    5    3   3   4                   compound                                                                             63    5      5      5     3      5    5    2   2   3                   (B)                                                                           Comparative                                                                          125   5      5      5     5      5    5    2   2   2                   compound                                                                             63    5      5      5     5      5    5    1   2   1                   (C)                                                                           Untreated                                                                            --    0      0      0     0      0    0    0   0   0                   __________________________________________________________________________

Test Example 2: Soil application test

A resin tray of an area of 600 cm2 was filled with andosol of volcanicash, followed by application of a fertilizer and subsequent sowing ofeach crop seed of corn, wheat and soybean, followed by soil covering ofabout 2 cm thickness. Furthermore, on the soil surface was placeduniformly the soil mixed with each weed seed of Chenopodium album,Polygonum lapathifolium, Brassica juncea, and Viola tricolor. Dilutionwith water of the wettable powder containing as the active ingredientthe compound of the present invention obtained by the FormulationExample 1 or the wettable powder individually containing as the activeingredients the Comparative Compounds (A), (B), and (C) shown in theTest Example 1 which were obtained in the same fashion as in theFormulation Example 1, was done. Subsequently, the diluted agents wereapplied to the soil surface uniformly with small power pressure sprayersat such amounts that the active ingredient contents might be 2.5, and1.25 kg/ha, individually.

The culture control was then continued in the greenhouse, and on day 21after the chemical application, observation was done about theherbicidal effect and the crop injury.

The results are shown in Table 4.

The assessment of the herbicidal effect and the crop injury wasrepresented following the criteria of the Test Example 1.

                                      TABLE 4                                     __________________________________________________________________________           Rate of                                                                             Herbicidal effect                                                Compound                                                                             application                                                                         Chenopodium                                                                          Polygonum                                                                            Brassica                                                                           Viola                                                                              Crop injury                              No.    kg/ha album  lapathifolium                                                                        juncea                                                                             tricolor                                                                           corn                                                                             wheat                                                                             soybean                           __________________________________________________________________________     7     2.5   5      5      5    5    0  0   0                                        1.25  5      4      4    5    0  0   0                                  8     2.5   5      5      5    5    0  0   1                                        1.25  5      4      5    5    0  0   0                                 10     2.5   5      5      5    5    0  2   1                                        1.25  5      5      5    5    0  0   0                                 14     2.5   5      5      5    5    0  1   1                                        1.25  5      5      4    5    0  0   0                                 21     2.5   5      5      5    5    0  0   0                                        1.25  5      5      4    4    0  0   0                                 23     2.5   5      5      5    5    0  0   0                                        1.25  5      4      3    5    0  0   0                                 26     2.5   5      5      5    5    0  0   0                                        1.25  5      5      4    5    0  0   0                                 38     2.5   5      5      5    5    0  0   1                                        1.25  5      5      5    5    0  0   0                                 Comparative                                                                          2.5   5      4      4    5    0  3   2                                 compound                                                                             1.25  4      4      2    3    0  0   0                                 (A)                                                                           Comparative                                                                          2.5   5      5      5    5    1  3   2                                 compound                                                                             1.25  5      5      4    5    0  1   0                                 (B)                                                                           Comparative                                                                          2.5   5      5      5    5    0  2   2                                 compound                                                                             1.25  5      5      4    5    0  1   1                                 (C)                                                                           Untreated                                                                            --    0      0      0    0    0  0   0                                 __________________________________________________________________________

Test Example 3: Submerged application test

A resin tray of an area of 400 cm² was filled with rice-field alluviumsoil, followed by application of a fertilizer and subsequent addition ofan appropriate amount of water for plowing. Inside a 0.5-cm layer fromthe soil surface was mixed each weed seed of Echinochloa crus-galli,Monochoria vaginalis, and Scirpus juncoides. On the soil surface wereplanted 4 tubers of Cyperus serotinus per tray.

Furthermore, 2 plants (three pieces/plant) of paddy-rice seedlings of2.3 leaf stage (species: Akinishiki) were transplanted in each of thetrays, followed by water injection, to keep a water filling depth ofabout 3.5 cm.

On day 5 after the weed seeding or the transplantation of the paddy-riceseedlings, the granules containing as the active ingredient the compoundof the present invention obtained by the Formulation Example 4 or thegranules containing as the active ingredients the Comparative Compounds(A), (B), and (C) shown in the Test Example 1 which were obtained in thesame fashion as in the Formulation Example 4, were subjected to fallingapplication to the water-filled surface at such amounts that the activeingredient contents might be 500, 250, and 125 g per 1 ha, individually.

The culture control was then continued in the greenhouse, and on day 21after the chemical application, observation was done about theherbicidal effect and the crop injury on the transplanted paddy-riceplants.

The results are shown in Table 5.

The assessment of herbicidal effect and crop injury on the transplantedpaddy-rice plants was represented following the criteria of the TestExample 1.

                                      TABLE 5                                     __________________________________________________________________________           Rate                                                                          of                        Crop injury                                         appli-                                                                            Herbicidal effect     transplanted                                 Compound                                                                             cation                                                                            Echinochloa                                                                         Monochoria                                                                          Scirpus                                                                            Cyperus                                                                            paddy-rice                                   No.    g/ha                                                                              crus-galli                                                                          vaginalis                                                                           juncides                                                                           serotinus                                                                          plant                                        __________________________________________________________________________    1      500 5     5     5    5    0                                                   250 3     5     4    4    0                                            2      500 5     5     5    5    0                                                   250 4     5     4    5    0                                            3      500 5     5     5    5    0                                                   250 4     5     4    5    0                                            7      250 5     5     5    5    1                                                   125 5     5     5    5    0                                            8      250 5     5     5    5    1                                                   125 4     5     5    5    0                                            9      250 5     5     5    5    1                                                   125 5     5     5    5    0                                            10     250 5     5     5    5    2                                                   125 5     5     5    5    0                                            16     500 5     5     5    5    0                                                   250 2     4     4    5    0                                            17     500 5     5     5    5    1                                                   250 4     5     4    5    0                                            22     250 5     5     5    5    1                                                   125 5     5     5    5    0                                            23     250 5     5     5    5    1                                                   125 5     5     5    5    0                                            26     250 5     5     5    5    1                                                   125 5     5     5    5    0                                            27     250 5     5     5    5    0                                                   125 4     5     4    5    0                                            33     250 5     5     5    5    0                                                   125 3     5     5    5    0                                            42     500 5     5     5    5    0                                                   250 4     5     4    5    0                                            43     500 5     5     5    5    1                                                   250 5     5     5    5    0                                            Comparative                                                                          250 4     5     3    5    1                                            compound                                                                             125 3     3     0    3    0                                            (A)                                                                           Comparative                                                                          250 5     5     5    5    4                                            compound                                                                             125 5     5     4    5    3                                            (B)                                                                           Comparative                                                                          250 5     5     5    5    4                                            compound                                                                             125 5     5     5    5    2                                            (C)                                                                           Untreated                                                                            --  0     0     0    0    0                                            __________________________________________________________________________

Test Example 4: Foliar application test (herbicidal effect)

An unglazed pottery of an area of 180 cm² was filled with andosol ofvolcanic ash, followed by application of a fertilizer, and then eachweed seed of Abutilon theophrasti, Xanthium strumarium, and Ipomoeapurpurea was seeded.

The culture control was continued in a greenhouse. The compound No.26 ofthe present invention and the Comparative Compounds (C), (D) and (E)were individually dissolved in acetone and a surfactant (Tween 20) toobtain 10% simple emulsions, which were then diluted with water so thatthe active ingredient contents might be 50, 25, 12.5, 6.3, and 3.1 g/ha,individually. The resulting solutions were applied to the foliage partof each weed with a small power pressure sprayer at an amount of 250liters for application to 1 ha, when Abutilon theophrasti seedlingsreached 4 to 4.5 leaf stage; Xanthium strumarium seedlings, 4.5 to 5leaf stage; Ipomoea purpurea seedlings, 3 to 3.5 leaf stage.

The culture control was thereafter continued in the greenhouse, toobserve the herbicidal effect on day 28 after the chemical application.

The results are shown in Table 6.

The herbicidal effect was evaluated visually, and represented on thebasis of the following criteria.

    ______________________________________                                        0                     No effect                                               25                    25% weed control                                        50                    50% weed control                                        75                    75% weed control                                        100                   completely killed                                       ______________________________________                                    

                                      TABLE 6                                     __________________________________________________________________________                                 Average value                                           Rate of                                                                            Herbicidal effect                                                                              of herbicidal                                           appli-                                                                             Abutilon         effect on                                               cation                                                                             theopa-                                                                             Xanthium                                                                            Ipomoea                                                                            three weed                                       Compound                                                                             g/ha rasti strumarium                                                                          purpurea                                                                           species                                          __________________________________________________________________________    No. 26 50   100.sup.1)                                                                          100   100  100                                                     25   100   100   100  100                                                     12.5 100   80    100  93                                                      6.3  100   20    90   70                                                      3.1  100   0     80   60                                               Comparative                                                                          50   100   100   100  100                                              compound                                                                             25   100   100   100  100                                              (C)    12.5 100   100   100  100                                                     6.3  100   70    80   83                                                      3.1  100   30    80   70                                               Comparative                                                                          50   100   100   100  100                                              compound                                                                             25   100   100   100  100                                              (D)    12.5 100   80    100  93                                                      6.3  100   20    90   70                                                      3.1  100   5     70   58                                               Comparative                                                                          50   100   100   100  100                                              compound                                                                             25   100   100   100  100                                              (E)    12.5 100   90    90   93                                                      6.3  100   10    75   63                                                      3.1  100   0     60   53                                               Untreated                                                                            --   0     0     0    0                                                __________________________________________________________________________     Note                                                                          .sup.1) 2 replications average value                                     

Test Example 5: Foliar application test (Crop injury)

An unglazed pottery of an area of 180 cm² was filled with andosol ofvolcanic ash, followed by application of a fertilizer, and then eachseed of corn (Pioneer species Sl15 ) and soybean (Williams 82) wasseeded per pot.

The culture control was continued in a greenhouse, and the compound No.26 of the present invention and the Comparative Compounds (C), (D) and(E) were individually dissolved in acetone and an activator (Tween 20)to obtain 10% simple emulsions, which were then diluted with water sothat the active ingredient contents might be 400,200,100, and 50 g/ha,individually. The resulting solutions were applied to the foliage partof each crop with a small power pressure sprayer at an amount of 250liters for application to 1 ha, when the growth leaf stage of thesubjective crops, namely corn and soybean, reached 3.8 to 4 leaf stageand 1.3 to 1.5 trifoliolate leaf stage, respectively.

The culture control was thereafter continued in the greenhouse, toobserve the crop injury on day 7 and 14 after the chemical application.

The results are shown in Table 7.

The crop injury was evaluated visually, and represented on the basis ofthe following criteria.

    ______________________________________                                        0                  No crop injury                                             25                 25% crop injury                                            50                 50% crop injury                                            75                 75% crop injury                                            100                Complete crop destruction                                  ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                                 Rate of                                                                       appli-                                                                        cation                                                               Compound g/ha      Corn injury                                                                              Soybean injury                                  ______________________________________                                        NO. 26   400       10.sup.1)                                                                             5.sup.2)                                                                            23.sup.3)                                                                            20.sup.4)                                      200       10      0     17     13                                             100       0       0     3      0                                              50        0       0     0      0                                     Comparative                                                                            400       55      40    47     43                                    compound 200       35      30    43     37                                    (C)      100       15      10    23     20                                             50        5       5     13     7                                     Comparative                                                                            400       50      40    40     33                                    compound 200       35      25    33     27                                    (D)      100       20      15    17     13                                             50        10      5     3      3                                     Comparative                                                                            400       20      15    40     37                                    compound 200       10      5     33     27                                    (E)      100       5       5     17     10                                             50        0       0     7      3                                     Untreated                                                                              --        0       0     0      0                                     ______________________________________                                         Note:                                                                         .sup.1) Initial crop injury (the result of the observation on day 7 after     chemical application; 2replications average value)                            .sup.2) Final crop injury (the result of the observation on day 14 after      chemical application; 2replications average value)                            .sup.3) Initial crop injury (the result of the observation on day 7 after     chemical application; 3replications average value)                            .sup.4) Final crop injury (the result of the observation on day 14 after      chemical application; 3replications average value)                       

Selectivity of the compound of the present invention on corn and soybean

From the Test Example 4, a chemical dose of each compound controlling90% of 3 species of weeds (ED₉₀) was calculated as an indicator forrepresenting the herbicidal activity. From the Test Example 5, achemical dose of each compound inhibiting 20% of the growth of corn orsoybean (ID₂₀) was calculated as an indicator for representing the cropinjury. By using these values, ID_(20/) ED₉₀ was calculated as anindicator representing the selectivity between the weeds and crops.

The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                                Herbicidal                                                                    effect  Crop injury*.sup.1                                                                         Selectivity                                              ED.sub.90                                                                             ID.sub.20 (g/ha)                                                                           (ID.sub.20 /ED.sub.90)                           Compound  (g/ha)    corn    soybean                                                                              corn soybean                               ______________________________________                                        No. 26    12        >400    300    >33  25                                    Comparative                                                                             9         130      80    14    9                                    compound                                                                      (C)                                                                           Comparative                                                                             12        100     150    8    13                                    compound                                                                      (D)                                                                           Comparative                                                                             13        370     130    28   10                                    compound                                                                      (E)                                                                           ______________________________________                                         Note                                                                          .sup.1) ID.sub.20 at initial crop injury                                 

As shown in the Test Examples described above, the compounds of thepresent invention not only have strong herbicidal activity, but also arefar more excellent than the known similar compounds from the respect ofsafety on crops. Thus, the compounds are useful as a herbicides.

What is claimed is:
 1. A tetrahydrofuran compound of the formula##STR77## wherein A represents a direct bond or a group represented by--B--CHR¹ -- wherein B represents oxygen atom, sulfur atom or imino andR¹ represents hydrogen atom or alkyl of C₁ -C₄ ;R represents hydrogen,halogen, hydroxyl, alkoxy of C₁ -C₄, benzyloxy, alkylsulfonyloxy of C₁-C₃ or a group represented by --O--COR² wherein R² represents alkyl ofC₁ -C₅, haloalkyl of C₁ -C₃, alkenyl of C₂ -C₅, cycloalkyl of C₃ -C₆,phenyl, benzyl, alkoxy of C₁ -C₄, alkylamino of C₁ -C₄ or dialkylaminoof C₂ -C₆ ; X represents halogen; Y represents hydrogen or halogen; andZ is a group represented by ##STR78## wherein U¹ represents oxygen orsulfur and R⁷ and R⁸ independently represent alkyl of C₁ -C₄.
 2. Atetrahydrofuran compound according to claim 1, wherein R representshydrogen, hydroxyl, benzyloxy, alkylsulfonyloxy of C₁ -C₃ or a grouprepresented by --O--COR² wherein R² represents alkyl of C₁ -C₅,haloalkyl of C₁ -C₃, alkenyl of C₂ -C₅, cycloalkyl of C₃ -C₆, phenyl, oralkoxy of C₁ C₄ ; and Z is a group represented by ##STR79## wherein U¹represents oxygen or sulfur.
 3. A tetrahydrofuran compound according toclaim 2, wherein R represents hydrogen, hydroxyl, alkylsulfonyloxy of C₁-C₃ or a group represented by --O--COR² wherein R² represents alkyl ofC₁ -C₅, alkenyl of C₂ -C₅, cycloalkyl of C₃ -C₆, phenyl, or alkoxy of C₁--C₄.
 4. A herbicidal composition which comprises a herbicidallyeffective amount of a tetrahydrofuran compound according to claim 1 anda suitable carrier therefor.
 5. A method for suppressing weed growth,comprising treating the plants or the growth soil thereof with aherbicidally effective amount of a tetrahydrofuran compound according toclaim 1.